U.S. patent number 6,699,947 [Application Number 10/070,805] was granted by the patent office on 2004-03-02 for method for producing phillips catalysts for polymerizing olefins with better productivity rates in the particle-form process.
This patent grant is currently assigned to Basell Polyolefine GmbH. Invention is credited to Paulus de Lange, Andreas Deckers, Kaspar Evertz, Guido Funk, Peter Kolle.
United States Patent |
6,699,947 |
Evertz , et al. |
March 2, 2004 |
Method for producing Phillips catalysts for polymerizing olefins
with better productivity rates in the particle-form process
Abstract
In a process for producing Phillips catalysts in which an oxidic
support material is treated in suspension with a chromium salt
solution and subsequently, after removing the solvent, calcined in
an oxygen-containing atmosphere at above 300.degree. C., the oxidic
support material and/or the catalyst after calcination are/is,
according to the present invention, comminuted until a mean
particle size of <100 .mu.m has been reached and the proportion
of particles having a size of <50 .mu.m is at least 30%,
preferably in the range from 40 to 80%. A process for preparing
homopolymers or copolymers of ethene in a loop reactor at from 30
to 150.degree. C. under a pressure in the range from 0.2 to 15 MPa
in the presence of a catalyst produced by the process of the
present invention is also provided.
Inventors: |
Evertz; Kaspar (Schifferstadt,
DE), Funk; Guido (Worms, DE), de Lange;
Paulus (Wesseling, DE), Kolle; Peter (Bad
Durkheim, DE), Deckers; Andreas (Flomborn,
DE) |
Assignee: |
Basell Polyolefine GmbH
(Wessling, DE)
|
Family
ID: |
7921414 |
Appl.
No.: |
10/070,805 |
Filed: |
March 11, 2002 |
PCT
Filed: |
August 31, 2000 |
PCT No.: |
PCT/EP00/08508 |
PCT
Pub. No.: |
WO01/17676 |
PCT
Pub. Date: |
March 15, 2001 |
Foreign Application Priority Data
|
|
|
|
|
Sep 9, 1999 [DE] |
|
|
199 43 206 |
|
Current U.S.
Class: |
526/106; 502/256;
526/348; 526/352; 502/319 |
Current CPC
Class: |
C08F
10/02 (20130101); B01J 23/26 (20130101); C08F
10/02 (20130101); C08F 4/24 (20130101); C08F
10/02 (20130101); C08F 2/14 (20130101); C08F
10/02 (20130101); C08F 4/025 (20130101); C08F
110/02 (20130101); C08F 110/02 (20130101); C08F
2500/12 (20130101); C08F 2500/18 (20130101) |
Current International
Class: |
C08F
10/02 (20060101); C08F 10/00 (20060101); B01J
23/16 (20060101); B01J 23/26 (20060101); C08F
110/02 (20060101); C08F 110/00 (20060101); C08F
004/24 (); C08F 010/02 (); B01J 021/08 (); B01J
023/26 () |
Field of
Search: |
;526/106,352,348
;502/256,319 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Lu; Caixia
Attorney, Agent or Firm: Keil & Weinkauf
Claims
We claim:
1. A process for producing Phillips catalysts in which an oxidic
support material is treated in suspension with a chromium salt
solution or a solution of chromium trioxide and subsequently, after
removing the solvent, calcined in an oxygen-containing atmosphere
at above 300.degree. C., wherein the oxidic support material before
calcination and/or the catalyst after calcination are/is comminuted
until a mean particle size of <100 .mu.m has been reached and
the proportion of particles having a size <50 .mu.m is at least
30% but not more than 80%.
2. A process as claimed in claim 1, wherein the oxidic support
material used is a silica gel which has a solids content,
calculated as silicon dioxide, in the range from 10 to 30% by
weight, and is largely spherical.
3. A process as claimed in claim 2, wherein the spherical silica
gel is prepared from spherical hydrosol which is treated with an
organic liquid selected from among alcohols having from 1 to 4
carbon atoms until at least 60% of the water present in the
hydrosol has been extracted, and the resulting dewatered hydrogel
is then dried at >160.degree. C. using an inert carrier gas
until the residual alcohol content is less than 10% by weight to
form the spherical silica gel.
4. A process as claimed in claim 3, wherein the dried silica gel is
loaded with chromium from a 0.05-5% strength by weight solution of
chromium trioxide in a ketone having from 3 to 5 carbon atoms or
from a 0.05-15% strength by weight solution of a chromium salt
compound which is converted into chromium trioxide under the
conditions of the calcination in an alcohol having from 1 to 4
carbon atoms and the solvent is subsequently evaporated under
reduced pressure.
5. A process as claimed in claim 1, wherein the calcination of the
chromium-laden oxidic support material is carried out in a
water-free gas stream containing at least 10% by volume of oxygen
for from 10 to 1,000 min at from 300 to 1,100.degree. C.
6. A process as claimed in claim 1, wherein the comminution of the
oxidic support material and/or of the catalyst material obtained
after calcination is carried out by dry milling using a ball mill
or in a beater mill.
7. A process as claimed in claim 1, wherein comminution is
continued until the proportion of particles having a size of <50
.mu.m is in the range from 40 to 80%.
8. A process for olefin polymerization in which homopolymers of
ethylene or copolymers of ethylene and a comonomer having from 3 to
12 carbon atoms in an amount of up to 10% by weight of comonomer
are prepared, wherein the polymerization is carried out in the
presence of a Phillips catalyst produced by a process as claimed in
claim 1 at from 30 to 150.degree. C. under a pressure in the range
from 0.2 to 15 MPa.
9. A process as claimed in claim 8, wherein the polymerization is
carried out as a precipitation polymerization in a loop reactor.
Description
The present invention relates to a process for producing Phillips
catalysts in which an oxidic support material is treated in
suspension with a chromium salt solution and subsequently, after
removing the solvent, calcined in an oxygen-containing atmosphere
at above 300.degree. C.
A process of this type is known and is comprehensively described
in, for example, DE-A 25 40 279. The catalysts produced as
described there are also comminuted and have particle sizes in the
range from 20 to 2,000 .mu.m, in particular from 40 to 300
.mu.m.
DE-A 36 40 802 and DE-A 36 40 803 state that restricting the oxidic
support to a particular, very narrow particle size distribution in
the range from 50 to 150 .mu.m gives chromium trioxide catalysts
which give polymers having an improved particle morphology at equal
or higher catalyst productivity.
Finally, it has been found in U.S. Pat. No. 5,641,842 that Phillips
catalysts having particle sizes of >75 .mu.m are advantageous
for the morphology of polyethylene prepared therewith.
After evaluation of the relevant literature, it can be said in
summary that classification of the oxidic support material
influences the catalyst productivity and the polyethylene
morphology. According to the literature, the best results are
generally achieved using relatively coarse catalysts, i.e. those
having particle sizes of >50 .mu.m.
It is an object of the present invention to provide a new process
which makes it possible to produce Phillips catalysts which further
increase the productivity of the polymerization of ethylene in loop
precipitation processes and, in particular, allow increased
polyethylene solids contents within the polymerization reactor.
We have found that this object is achieved by a process of the
generic type mentioned at the outset, whose defining features are
that the oxidic support material before calcination and/or the
catalyst after calcination are/is comminuted until a mean particle
size of <100 .mu.m has been reached and the proportion of
particles having a size of <50 .mu.m is at least 30%.
According to the present invention, the oxidic support material
used is a silica gel which has a solids content, calculated as
silicon dioxide, in the range from 10 to 30% by weight, preferably
from 11 to 25% by weight, and is largely spherical. Such a silica
gel is obtained by introducing a solution comprising sodium water
glass or potassium water glass into a twisting stream of a mineral
acid longitudinally and tangentially to the flow direction of the
stream and spraying the silicic acid hydrosol formed into a gaseous
medium so as to form droplets. The sprayed hydrosol then solidifies
in the gaseous medium to form spherical particles and is freed of
adhering salts by washing with water.
The spherical hydrosol is then treated with an organic liquid
selected from among alcohols having from 1 to 4 carbon atoms until
at least 60% of the water present in the hydrosol has been
extracted. The dewatered hydrogel which has been treated with the
alcoholic liquid is then dried until at >160.degree. C. using an
inert carrier gas the residual alcohol content is less than 10% by
weight.
The xerogel obtained in this way is then loaded with chromium from
a 0.05-5% strength by weight solution of chromium trioxide in a
ketone having from 3 to 5 carbon atoms or from a 0.05-15% strength
by weight solution of a chromium compound which is converted into
chromium trioxide under the conditions of the calcination in an
alcohol having from 1 to 4 carbon atoms and the solvent is
subsequently evaporated under reduced pressure.
For the calcination, the chromium-laden oxidic support material is
maintained at from 300 to 1,100.degree. C. in a water-free,
oxygen-containing gas stream for from 10 to 1,000 minutes.
The comminution according to the present invention of the oxidic
support material or of the catalyst material obtained as described
above is carried out by dry milling using a ball mill or in a
beater mill as described, for example, in DE-A 36 40 802. The
milling time necessary to achieve the desired particle size is
determined by taking samples at particular time intervals.
In the olefin polymerization in which the catalyst produced
according to the present invention is used, it is possible to
prepare homopolymers of ethylene or copolymers of ethylene with a
comonomer having from 3 to 12 carbon atoms in an amount of up to
10% by weight of comonomer. The polymerization itself is carried
out at from 30 to 150.degree. C. under a pressure in the range from
0.2 to 15 MPa.
It has surprisingly been found that, at a constant reactor output,
the Phillips catalysts having a particle size of <100 .mu.m used
according to the present invention result in an increase in the
average residence time of the catalyst in the reactor and that the
catalyst productivity increases at the same time. The higher
catalyst productivity presumably results from significantly higher
polyethylene solids concentrations being able to be achieved in the
loop precipitation process, particularly in loop reactors, when
using the catalysts produced according to the present invention
than when using the catalysts described in the literature, which
customarily have particle sizes of >100 .mu.m. Furthermore, it
has surprisingly been found that the Phillips catalysts produced
according to the present invention make it possible to achieve
comparable results in terms of the morphology of the polyethylene
prepared therewith to those obtained using the conventional
catalysts having particle sizes of >100 .mu.m.
The process of the present invention gives particularly optimal
results when the proportion of particles having a size of <50
.mu.m is in the range from 40 to 80%.
For the purposes of the present invention, all particle size data
were determined in accordance with DIN 53 477, sieve analysis.
The examples and comparative examples described below show that in
the case of the catalysts described in the literature formation of
deposits on the reactor wall occurs even at relatively low PE
solids contents above 40% by weight, while the catalysts produced
according to the present invention allow solids contents of about
60% without reactor fouling in loop reactors.
Production of the oxidic support material:
EXAMPLE 1 (according to the present invention)
The catalyst support was produced as described in DE-A 36 40 802,
except that the dried xerogel spheres were milled by means of a
beater mill to a mean particle size in the range from 1 to 100
.mu.m and were sieved so that the proportion of particles having a
size of <50 .mu.m was 80%.
EXAMPLE 2 (according to the present invention)
The catalyst support was produced as described in Example 1, except
that the proportion of particles having a size of <50 .mu.m was
only 30%.
EXAMPLE 3 (comparative example)
The catalyst support was produced as described in Example 1, except
that the proportion of particles having a size of <50 .mu.m was
only 15%.
EXAMPLE 4 (comparative example)
The catalyst was produced as described in Example 1 of DE-A 36 40
802 (page 7, line 15). The support particles had a mean particle
size in the range from 50 to 100 .mu.m (page 8, line 26).
EXAMPLE 5 (comparative example)
The catalyst was produced as described in Comparative Experiment 1
in DE-A 36 40 802 (page 9, line 16). The support particles had a
mean particle size in the range from 1 to 300 .mu.m.
Production of catalysts 1-4:
Catalyst 1
Catalyst 1 was produced as described in Example 1 of DE-A 36 40 802
(page 8, line 31), except that 15 kg of the oxidic support material
from Example 1 were used.
Catalyst 2
Catalyst 2 was produced as described in Example 1 of DE-A 36 40 802
(page 8, line 31), except that 15 kg of the oxidic support material
from Example 2 were used.
Comparative catalyst 3
Comparative catalyst 3 was produced as described in Example 1 of
DE-A 36 40 802 (page 8, line 31), except that 15 kg of the oxidic
support material from Example 3 were used.
Comparative catalyst 4
Comparative catalyst 4 was produced as described in Example 1 of
DE-A 36 40 802 (page 8, line 31) using 15 kg of the oxidic support
material from Example 4, as described in DE-A 36 40 802.
Comparative catalyst 5
Comparative catalyst 5 was produced as described in Example 1 of
DE-A 36 40 802 (page 8, line 31) using 15 kg of the oxidic support
material from Example 5, as described in DE-A 36 40 802.
Polymerization:
For the polymerization of ethylene, use was made of a customary and
known loop reactor whose reaction space consisted of a tube circuit
having a capacity of 6 m.sup.3. At a pressure of 4.0 MPa, the
reaction space contained a suspension comprising liquid i-butane,
solid polyethylene, 6% by weight of dissolved ethene and 0.4% by
weight of dissolved 1-hexene. The polymerization temperature was
from 103.5 to 103.8.degree. C.
The suspension was pumped around the reactor by means of a
propeller pump operating at 3,000 rpm. At a constant reactor output
of 900 kg of PE/h, attempts were made to increase the polyethylene
solids content in the suspension as far as possible. The achievable
PE solids contents were limited by occurrence of reactor fouling
(formation of deposits on the reactor walls or increases in the
power drawn by the propeller pump).
The following table shows the results achieved using the catalysts
1 to 5:
Cat. 1 Cat. 2 Cat. 3 Cat. 4 Cat. 5 Max. PE solids 58 56 40 38 39
content in the reactor (% by weight) Catalyst 12,450 11,750 6950
7200 6650 productivity (kg of PE/kg of cat.) Melt index HLMI 6.2
6.4 6.5 6.2 6.4 190.degree. C./21.6 kp in accordance with DIN 53735
(g/10 min) Bulk density in 500 500 490 500 480 accordance with DIN
53468 (g/l) Sieve analysis in accordance with DIN 53457 <125
.mu.m (%) 0.5 0.6 0.4 0.4 0.6 >2000 .mu.m (%) 0.2 0.3 0.2 0
0.5
Significantly higher PE solids contents in the loop reactor can be
achieved when using the catalysts produced according to the
invention, as a result of which the catalyst productivities
increase significantly. In the cases of comparative catalysts 3 to
5, attempts to increase the PE solids contents to more than 40% by
weight failed due to reactor fouling.
The bulk density of the polyethylene and the proportion of fumes
and of coarse material <125 .mu.m, >2000 .mu.m) are virtually
unchanged in the examples according to the present invention and
are at the same level as those in the comparative examples.
* * * * *